An intramolecular cascade reaction consisting of a formal anti-carbopalladation terminated by the ring-opening of a cyclopropanol unit is presented. The products, which involve tetrasubstituted alkene units embedded in an oligocyclic ring system, are generated in moderate to excellent yield. The opening of the cyclopropanol unit leads to a keto group in the γ-position to the emerging double bond.
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http://dx.doi.org/10.1021/acs.orglett.8b03179 | DOI Listing |
Org Lett
August 2024
College of Chemistry and Chemical Engineering, Yantai University, Yantai, 264005, People's Republic of China.
A cascade reaction of cyclopropyl alcohols, DABSO (1,4-diazoniabicyclo[2.2.2]octane-1,4-disulfinate), and -(sulfonyl)acrylamides has been developed.
View Article and Find Full Text PDFNat Commun
September 2023
Chongqing Key Laboratory of Natural Product Synthesis and Drug Research, Innovative Drug Research Center, School of Pharmaceutical Sciences, Chongqing University, Chongqing, 401331, China.
Sarpagine alkaloids offer signicant opportunities in drug discovery, yet the efficient total syntheses and diverse structural modifications of these natural products remain highly challenging due to the architectural complexity. Here we show a homo-Mannich reaction of cyclopropanol with imines generated via a Bischler-Napieralski reaction enables a protecting-group-free, redox economic, four-step access to the tetracyclic sarpagine core from L-tryptophan esters. Based on this advancement, diversified syntheses of sarpagine alkaloids and analogues are achieved in a short synthetic route.
View Article and Find Full Text PDFNat Chem
August 2022
Department of Biomolecular Chemistry, Leibniz Institute for Natural Product Research and Infection Biology - Hans Knöll Institute (Leibniz-HKI), Jena, Germany.
Bacteria of the Burkholderia pseudomallei (BP) group pose a global health threat, causing the infectious diseases melioidosis, a common cause of pneumonia and sepsis, and glanders, a contagious zoonosis. A trait of BP bacteria is a conserved gene cluster coding for the biosynthesis of polyketides (malleicyprols) with a reactive cyclopropanol unit that is critical for virulence. Enzymes building this warhead represent ideal targets for antivirulence strategies but the biochemical basis of cyclopropanol formation is unknown.
View Article and Find Full Text PDFOrg Lett
October 2021
Department of Chemistry, Renmin University of China, Beijing 100872, China.
The ring opening of cyclopropanols is rarely used in multicomponent reactions. Herein we report the three-component reaction of cyclopropanols with alkenes and -butyl hydroperoxide (TBHP) catalyzed by an iron catalyst. This protocol enables the incorporation of both the β-carbonyl fragment and a peroxy unit across the C═C double bond regioselectively, thus allowing an efficient, facile access to 5-oxo peroxides.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
August 2020
Department of Biomolecular Chemistry, Leibniz Institute for Natural Product Research and Infection Biology (HKI), Beutenbergstrasse 11a, 07745, Jena, Germany.
Pathogenic bacteria of the Burkholderia pseudomallei group cause severe infectious diseases such as glanders and melioidosis. Malleicyprols were identified as important bacterial virulence factors, yet the biosynthetic origin of their cyclopropanol warhead has remained enigmatic. By a combination of mutational analysis and metabolomics we found that sulfonium acids, dimethylsulfoniumpropionate (DMSP) and gonyol, known as osmolytes and as crucial components in the global organosulfur cycle, are key intermediates en route to the cyclopropanol unit.
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